Dehydrogenation over catalyst of pd on molecular sieve treated with aluminum monofluoride vapor



United States Patent Ofiice 3,383,431 Patented May 14, 1968 3,383,431 DEHYDROGENATION OVER CATALYST F Pd 0N MOLECULAR SIEVE TREATED WITH ALU- MINUM MONOFLUORIDE VAPOR Norman A. Fishel, Lansing, Mich., assignor to Universal Oil Products Company, Des Plaines, 11]., a corporation of Delaware No Drawing. Filed June 30, 1967, Ser. No. 650,228 Claims. (Cl. 260-6833) ABSTRACT OF THE DISCLOSURE A paraffinic hydrocarbon is dehydrogenated untilzing a catalyst comprising a crystalline aluminosilicate chemically combined with a metal subfluoride vapor.

DESCRIPTION OF THE INVENTION This invention relates to a conversion process for the dehydrogenation of a parafiinic hydrocarbon into more useful compounds. More specifically, this invention is concerned with a conversion process for the dehydrogenation of a paratfinic hydrocarbon utilizing a novel catalyst comprising a crystalline aluminosilicate containing at least one metal from Group VIII of the Periodic Table chemically combined with a metal subfluoride vapor.

It is an object of this invention to provide a process for the dehydrogenation of paraflinic hydrocarbons utilizing a novel dehydrogenation catalyst.

A specific object of this invention is to provide a novel method and a novel catalyst for dehydrogenating paraffinic hydrocarbons to provide the desired dehydrogenated product in high yields without the inducing of other decomposition reactions.

One embodiment of the invention relates to a conversion process which comprises dehydrogenating a paraffinic hydrocarbon at a temperature in the range of from about 0 to about 485 C. and a pressure in the range of from about atmospheric to about 200 atmospheres in contact with a catalyst comprising a crystalline aluminosilicate containing at least one metal from Group VIII of the Periodic Table chamically combined with a metal subfluoride vapor.

Other objects and embodiments referring to alternative paraffinic hydrocarbons and to alternative catalytic compositions of matter will be found in the following detailed description of the invention.

The process of my invention is especially applicable to the dehydrogenation of paraflinic hydrocarbons including the cycloparaffins. Suitable parafiinic hydrocarbons thus would include propane, n-butane, isobutane, npentane, isopentane and higher molecular weight paraffinic hydrocarbons and mixtures thereof. It is not intended to limit this invention to those enumerated paraflinic hydrocarbons set out above as it is contemplated that paraffinic hydrocarbons containing up to about 20 carbon atoms per molecule may he dehydrogenated according to the process of the present invention.

As hereiubefore set forth, the invention is concerned with a conversion process for the dehydrogenation of paraflinic hydrocarbons, said process being effected in the presence of a catalyst which possesses a high degree of hydrocarbon conversion activity and is particularly effective as a dehydrogenation catalyst for the paratiinic hydrocarbons hereinabove set forth. As hereinbefore set forth, the catalyst comprises a crystalline aluminosilicate containing at least one metal from Group VIII of the Periodic Table combined with a metal subfluoride vapor. The crystalline aluminosilicates are composed of Sil, and A10 tetrahedra, a silicon or aluminum atom being centered around four oxygen atoms in the tetrahedra and the oxygen being shared with other surrounding tetrahedra. These aluminosilicates are geometrically arranged to form a pore structure having sufficiently large pore size to permit the reactant molecules to pass into said port structure. Preferably, the aluminosilicates employed in the catalyst support have pore sizes of from about 4 up to about 15 angstroms in cross-sectional diameter. The aluminosilicates are treated to improve their catalytic activity by techniques such as ion-exchange with suitable cations and thermal treatment. Ordinarily, the aluminosilicates are synthetically prepared in the alkali metal form (usually sodium) and there is one monovalent alkali metal cation associated with each aluminum centered tetrahedra (to maintain electrical neutrality). The aluminosilicates may be ion-exchanged with polyvalent cations such as calcium, magnesium, beryllium, rare earths, etc., to replace a substantial amount of the monovalent cations. This causes one polyvalent cation to be associated with more than one aluminum centered tetrahedra and if these tetrahedra are spread sufliciently far apart (due to the presensence of silicon centered tetrahedra), areas of local electrical charge will be formed which aid in promoting catalytic reactions. Another treating technique to improve the catalytic activity of the aluminosilicates is to ionexchange with ammonium ions followed by thermal treatment, preferably above 300 C. to convert the crystalline aluminosilicates to the hydrogen form.

There are numerous types of crystalline aluminosilicates, both synthetic and natural occurring. It is preferable that the pore mouths of the crystalline aluminosilicates have cross-sectional diameters of from about 4 to 15 angstrom units. Among the preferable crystalline aluminosilicates that are suitable are the hydrogen and/ or polyvalent forms of faujasite, and mordenite, and especially preferable is the hydrogen form of mordenite. The concentration of crystalline aluminosilicate may be as high as or the crystalline aluminosilicate may be held with a matrix which may be selected from the group consisting of silica, alumina, and silica-alumina mixtures.

As set forth hereinabove, the catalyst comprises a crystalline aluminosilicate containing at least one metal from Group VIII of the Periodic Table that is combined with a metal subfluoride vapor to etfect combination of said crystalline aluminosilicate with the metal subfluoride. Typical metals from Group VIII of the Periodic Table for use in the present invention thus includes iron and the platinum group metals including platinum, palladium, ruthenium, rhodium, osmium and iridium and mixtures thereof. It is preferred that the Group VIII component of my novel catalyst be selected from the group consisting of nickel, platinum, and palladium. The Group VIII component will normally be utilized in an amount of from about 0.01 to about 2.0 percent by weight. Particularly preferred metal subfiuorides for use in my invention include the aluminum subfiuorides including silicon difiuoride due mainly to the relative ease in preparing these compounds although the invention is not restricted to their use but may employ any of the known metal subfluorides insofar as they are adaptable. However, it is not intended to infer that ditferent metal subfiuorides which may be employed will produce catalysts which have identical eifects upon any given organic reaction as each of the catalysts produced from different metal subfiuorides and by slightly varying procedures will exert its own characteristic action.

The catalyst of the present invention comprises a crys talline aluminosilicate containing at least one metal from Group VIII of the Periodic Table combined with the metal subfluoride vapor so as to effect combination of said crystalline aluminosilicate with the metal subfluoride vapor and it is the particular association of these components which results in the unusual catalytic properties of this catalyst. The metal subfluoride vapor may be combined with the crystalline aluminosilicate at temperatures in the range of 650 C. to about 1000 C. and at a pressure of from about subatmospheric to about 10 atmospheres. The formation of the metal subtluoride vapor, and especially the formation of aluminum monofluoride is accomplished by sweeping with a gas such as helium, argon or hydrogen, and preferably helium, a stoichiometric mixture of aluminum metal (melting point about 660 C.) and aluminum trifluoride (melting point greater than 1000 C.) which is heated to about 750 to 850 C. The crystalline aluminosilicate containing at least one metal from Group VIII of the Periodic Table which is then chemically combined with aluminum monofluoride is placed in the downstream helium flow. The chemical combination takes place at temperatures in excess of 650 C. Fluoride concentrations of between 0.01 percent to about 5 percent (by weight) are preferred.

In an alternative method, the catalyst may be prepared by pelleting a mixture of aluminum powder with a stoichiometric excess of aluminum trifluoride, and mixing these pellets with the crystalline aluminosilicate containing at least one metal from Group VIII of the Periodic Table and then heating this support in vacuum in a furnace tube at elevated temperatures.

The process of this invention utilizing the catalyst hereinbefore set forth may be etfected in any suitable manner and may comprise either a batch or a continuous type operation. The preferred method by which the process of this invention may be eflected in a continuous type operation. One particular method is the fixed bed operation in which the paraflinic hydrocarbon is continuously charged to a reaction zone containing a fixed bed of the desired catalyst, said zone being maintained at the proper operating conditions of temperature and pressure, that is, 'a temperature in the range of from about 0 to about 425 C. or more, and preferably from 50 to about 400 C., and a pressure including a. pressure of from about atmospheric to about 200 atmospheres or more. The catalyst is suitable for either :gas phase or liquid phase reactions so that the liquid hourly space velocity (the volume of charge per volume of catalyst per hour) may be maintained in the reaction zone in the range of from about 0.1 to about 20 or more, preferably in the range of from about 0.1 to about 10, or at a gaseous hourly space velocity in the range of from about 100 to about 3000 or more. The reaction zone may comprise an unpacked vessel or coil or may be lined with an adsorbent packing material. The charge passes through the catalyst bed in an upward, downward or radial flow and the dehydrogenated product is continuously withdrawn, separated from the reactor eflluent, and recovered, while any unreacted starting materials may be recycled to form a portion of the feed stock. It is also contemplated within the scope of this invention that gases such 'as helium, hydrogen, nitrogen, argon, etc., may also be charged to the reaction zone if desired. Another continuous type operation comprises the moving bed type in which the paraflinic hydrocarbon and the catalyst bed move either concurrently or countercurrently to each other while passing through said reaction zone.

Still another type of operation which may be used is the batch type operation in which a quantity of the parafflnic hydrocarbon and the catalyst are placed in an appropriate apparatus such as, for example, a rotating or stirred autoclave. The apparatus is then heated to the desired temperature and maintained thereat for a predetermined residence time at the end of which time the flask and contents thereof are cooled to room temperature and the desired reaction product is recovered by conventional means, such 'as, for example, by washing, drying, fractional distillation, crystallization, etc.

The following examples are introduced for the purpose Example I A quartz vessel with provisions for connection to a vacuum system is filled with a mixture of about grams of a 5A crystalline aluminosilicate containing about 0.5 weight percent palladium and having a 2:1 silica to alumina mol ratio and about 26 grams of Va inch pellets comprising about 20% aluminum metal and about 80% aluminum tritiuoride by weight. The contents of the vessel were outgassed at a pressure of less than 10 mm. while slowly being heated in a tube furnace. Approximately 4 /2 hours were allowed for the system to reach 600 to about 650 C. The evacuated vessel Was then sealed off. The vessel was then placed in a muflle furnace at 750 C. for 1 hour and rotated slowly to aid mixing.

The sealed vessel was cooled to room temperature. After cooling, the vessel was opened in a helium dry box, the somewhat greyish catalyst spheres were separated from the pellets and the catalyst was then placed in vessels which were then sealed. This catalyst is designated as catalyst A.

Example II In this example, a volatile fluoride (800 C.) is prepared by sweeping with helium a stoichiomctric mixture of aluminum metal (melting point 660 C.) and aluminum trilluoride (melting point greater than 1000 C.) which is heated to 750-800 C. Aluminum monofiuoride is then produced. A catalyst base in the form of hydrogen form faujasite as inch diameter pills containing about 0.75 weight percent platinum is then placed in the downstream helium flow and the aluminum monofluoride is chemically combined with the base at a temperature in excess of 650 C.

The catalyst produced by this vapor deposition and chemical combination of the aluminum monofiuoride with the hydrogen form faujasite containing platinum has fluride levels of less than 5 percent by weight fluoride chemically combined therewith. This catalyst is designated as catalyst B.

Example III A volatile fluoride (800 C.) is prepared by sweeping with helium a stoichiometric mixture of aluminum metal (melting point 660 C.) and aluminum trifluoride (melting point greater than 1000 C.) which is heated to 750- 800 C. Aluminum monofluoride is then produced. A catalyst base in the form of hydrogen form mordenite A inch diameter spheres containing about 0.75 weight percent platinum are prepared and placed in the downstream helium flow and the aluminum monofluoride is chemically combined with the base at a tcmperature in excess of 650 C.

The catalyst produced by this vapor deposition and chemical combination of the aluminum monofluoride with the hydrogen form mordenite containing platinum has fluoride levels of less than 5 Weight percent of fluoride chemically combined therewith. This catalyst is designated as catalyst C.

Example IV The catalyst designated as catalyst A prepared according to Example I above is utilized in a dehydrogenation reaction, the finished catalyst being placed in an appropri ate continuous dehydrogenation apparatus. In the experiment, normal butane is charged to the dehydrogenation zone. The reactor is maintained at about 50 p.s.i.g. and C. Substantial conversion of the normal butane to C olefins is obtained as is evidenced by gas-liquid chromatography.

Example V The catalyst prepared according to Example II and designated as catalyst B is utiiized in an appropriate continuous dehydrogenation apparatus. In the experiment, the finished catalyst is placed in the reaction zone and normal pentane is charged to said reaction zone. The reactor is maintained at about 100 psig and about 210 C. Substantial conversion of the normal pentane to C olefins is obtained as is evidenced by gas-liquid chromatography.

Example Vi The catalyst prepared according to Example III and designated as catalyst C is utilized in an appropriate continuous dehydrogenation apparatus to determine the dehydrogenation activity of said catalyst. In the experiment, the catalyst is placed in the dehydrogenation reaction zone and normal hexane is charged to said reaction zone. The reactor is maintained at about 45 p.s.i.g. and a temperature of about 160 C. Gas-liquid chromatographic analyses of the product stream indicate that substantial conversion to heXene-Z is obtained.

1 claim as my invention:

1. A conversion process which comprises dehydrogenating a parafiinic hydrocarbon at a temperature in the range of from about 0 to about 425 C. and a pressure in the range of from about atmospheric to about 200 atmospheres in contact with a catalyst comprising a crystalline aluminosilicate containing at least one metal from Group VIII of the Periodic Table treated with a metal subfiuoride vapor.

2. The process of claim 1 further characterized in that said metal subfiuoride is aluminum monofluoride and that said crystalline aluminosilicate contains silica and alumina tetrahedra having uniform pores of between 4 and 15 angstroms.

3. The process of claim 2 further characterized in that said silica and alumina tetrahedra having uniform pores of between 4 and 15 angstroms are suspended in an alumina matrix.

4. The process of claim 2 further characterized in that said silica and alumina tetrahedra having uniform pores of between 4 and 15 angstroms are suspended in a silica iatrix.

5. The process of claim 2 further characterized in that said silica and alumina tetrahedra having uniform pores of between 4 and 15 angstroms are suspended in a silicaalumina matrix.

6. The process of claim 2 further characterized in that said crystalline aluminosilicate is the hydrogen form of faujasite and the Group VIII metal is selected from the group consisting of nickel, platinum and palladium.

7. The process of claim 2 further characterized in that said crystalline aluminosilicate is the hydrogen form of mordenite and the Group VIII metal is selected from the group consisting of nickel, platinum and palladium.

8. The process of claim 2 further characterized in that said paraflinic hydrocarbon is isobutane.

9. The process of claim 2 further characterized in that said paraflinic hydrocarbon is normal butane.

1G. The process of claim 2 further characterized in that said paraffinic hydrocarbon is normal pentane.

References Cited UNITED STATES PATENTS 3,126,426 3/-964 Turnquest et a1. 260683.3 3,315,008 4/1967 Abell et a1 260-6833 3,332,886 7/1967 Wilson 252442 3,338,843 8/1967 Goble et al 252-442 DELBERT E. GANTZ, Primaly Examiner.

G. E. SCHMITKONS, Assistant Examiner. 

